CN116806319A - Polarizing plate and method for producing polarizing plate - Google Patents
Polarizing plate and method for producing polarizing plate Download PDFInfo
- Publication number
- CN116806319A CN116806319A CN202280013779.3A CN202280013779A CN116806319A CN 116806319 A CN116806319 A CN 116806319A CN 202280013779 A CN202280013779 A CN 202280013779A CN 116806319 A CN116806319 A CN 116806319A
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- polarizing plate
- layer
- resin film
- laminate
- main surface
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/16—Chemical modification with polymerisable compounds
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- G02B1/14—Protective coatings, e.g. hard coatings
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Abstract
Provided is a polarizing plate wherein discoloration is suppressed. The polarizing plate according to the embodiment of the present invention is composed of a resin film containing iodine and having a first main surface and a second main surface facing each other, wherein the resin film has a chemically modified portion on an end surface, and the chemical modified portion has a higher hydrophobicity than other portions not chemically modified.
Description
Technical Field
The present invention relates to a polarizing plate and a method for manufacturing the polarizing plate.
Background
Image display devices typified by liquid crystal display devices and Electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) are rapidly spreading. A polarizing plate is typically used for an image display panel mounted on an image display device. A polarizing plate with a retardation layer, which is formed by integrating a polarizing plate and a retardation plate, is widely used in practice (for example, patent document 1). However, the polarizing plate included in the polarizing plate is subjected to severe environments (e.g., high temperature and high humidity environments) for a long period of time to cause discoloration (color separation), and the polarizing performance in the discoloration portion is sometimes lowered.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 3325560
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above problems, and its main object is to provide: a polarizing plate in which occurrence of discoloration is suppressed.
Solution for solving the problem
According to an embodiment of the present invention, there is provided a polarizing plate. The polarizing plate is composed of a resin film containing iodine and having a first main surface and a second main surface which are opposed to each other, wherein the resin film has a chemically modified part on an end surface, and the chemical modified part has a higher hydrophobicity than other parts which are not chemically modified.
In one embodiment, the chemical modification portion contains a group containing fluorine.
In one embodiment, the fluorine-containing group includes a trifluoroacetyl group.
In one embodiment, the chemical modification unit is chemically modified with trifluoroacetic anhydride.
In 1 embodiment, the end face is 1787cm in FT-IR spectrum measured by ATR -1 The absorbance at 2940cm -1 The ratio of absorbance under the condition exceeds 0.2.
In one embodiment, the end portion including the end face includes fluorine.
In one embodiment, the chemical modification unit is chemically modified with a silylating agent.
In one embodiment, the end portion including the end face includes silicon.
In one embodiment, the polarizing plate includes a cover portion that covers an end surface of the resin film.
According to another embodiment of the present invention, there is provided a method for manufacturing the above-described polarizing plate. The manufacturing method comprises the following steps: preparing a laminate having a resin film containing iodine and having a first main surface and a second main surface facing each other, a first protective material disposed on the first main surface, and a second protective material disposed on the second main surface; and chemically modifying an end face of the resin film of the laminate.
According to still another embodiment of the present invention, there is provided a polarizing plate. The polarizing plate has at least one of the above-mentioned polarizing plate and a protective layer or a retardation layer.
According to still another embodiment of the present invention, there is provided a method for manufacturing the polarizing plate. The manufacturing method comprises the following steps: preparing a laminate having a resin film containing iodine and having a first main surface and a second main surface facing each other, a first protective material disposed on the first main surface, and a second protective material disposed on the second main surface; and chemically modifying an end face of the resin film of the laminate, wherein the protective material includes at least one of the protective layer and the retardation layer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, by forming the chemical modification portion, a polarizing plate in which occurrence of discoloration is suppressed can be obtained.
Drawings
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to 1 embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view showing the outline of the structure of a laminate used for manufacturing a polarizing plate according to the first embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view showing the outline of the structure of a laminate used in the production of a polarizing plate according to the second embodiment of the present invention.
Fig. 4A is an observation photograph showing the evaluation result of the durability of example 2-1.
Fig. 4B is an observation photograph showing the evaluation result of the durability of example 2-2.
Fig. 4C is an observation photograph showing the evaluation result of the durability of comparative example 2.
FIG. 5 is a graph showing FT-IR spectra corresponding to examples 1-1, 1-2, 1-3 and comparative example 1.
FIG. 6 is a cross-sectional SEM photograph (magnification: 5) of an end portion of a polarizing plate having a retardation layer of example 2-1.
Detailed Description
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
(definition of terms and symbols)
The terms and symbols in the present specification are defined as follows.
(1) Refractive index (nx, ny, nz)
"nx" is a refractive index in a direction in which the in-plane refractive index becomes maximum (i.e., a slow axis direction), "ny" is a refractive index in a direction orthogonal to the slow axis (i.e., a fast axis direction), and "nz" is a refractive index in a thickness direction.
(2) In-plane phase difference (Re)
"Re (λ)" is the in-plane retardation measured with light of wavelength λnm at 23 ℃. For example, "Re (550)" is the in-plane retardation measured with light having a wavelength of 550nm at 23 ℃. When the thickness of the layer (thin film) is d (nm), re (λ) is represented by the formula: re (λ) = (nx-ny) ×d.
(3) Retardation in thickness direction (Rth)
"Rth (λ)" is a phase difference in the thickness direction measured with light having a wavelength of λnm at 23 ℃. For example, "Rth (550)" is a phase difference in the thickness direction measured with light having a wavelength of 550nm at 23 ℃. When the thickness of the layer (thin film) is d (nm), rth (λ) is represented by the formula: rth (λ) = (nx-nz) ×d.
(4) Nz coefficient
The Nz coefficient is obtained from nz=rth/Re.
(5) Angle of
When referring to an angle in this specification, the angle includes both clockwise and counterclockwise with respect to a reference direction. Thus, for example, "45" means ± 45 °.
A. Polarizing plate
Fig. 1 is a schematic cross-sectional view of a polarizing plate according to 1 embodiment of the present invention. In fig. 1, the cross section of the polarizing plate is not hatched for easy viewing of the drawing. The polarizing plate 10 is composed of a resin film having a first main surface 10a and a second main surface 10b facing each other. The resin film has a chemically modified portion chemically modified at the end face 10c of the polarizing plate 10. The chemical modification portion is not particularly limited as long as it is formed on at least a part of the end face 10c, and the formation region is formed entirely over the end face 10c, for example.
The polarizing plate is composed of a resin film containing iodine. As the resin film, for example, a hydrophilic polymer film such as a polyvinyl alcohol (PVA) film, a partially formalized PVA film, or an ethylene-vinyl acetate copolymer partially saponified film is used.
The thickness of the polarizing plate 10 is preferably 15 μm or less, may be 12 μm or less, may be 10 μm or less, and may be 8 μm or less. On the other hand, the thickness of the polarizing plate is preferably 1 μm or more.
The polarizing plate 10 preferably exhibits absorption dichroism at any wavelength of 380nm to 780 nm. The single-sheet transmittance (Ts) of the polarizing plate 10 is preferably 41.0% or more, more preferably 42.0% or more, and still more preferably 42.5% or more. On the other hand, the single-sheet transmittance of the polarizing plate 10 is, for example, 44.2% or less. The polarization degree (P) of the polarizing plate 10 is preferably 99.95% or more, more preferably 99.98% or more, and still more preferably 99.99% or more. On the other hand, the polarization degree of the polarizing plate 10 is, for example, 99.996% or less.
The single-sheet transmittance is typically a Y value obtained by performing visibility correction by measurement with an ultraviolet-visible spectrophotometer. The degree of polarization is typically determined as follows: the parallel transmittance Tp and the orthogonal transmittance Tc, which are subjected to visibility correction, are measured by an ultraviolet-visible spectrophotometer, and are obtained from the following equation.
Polarization (%) = { (Tp-Tc)/(tp+tc) } 1/2 ×100
The hydrophobicity of the chemically modified portion is higher than the hydrophobicity of other portions (e.g., the main surface) that are not chemically modified. By forming such a chemically modified portion, the intrusion of water into the polarizing plate (resin film) is suppressed, and a polarizing plate (polarizing plate) in which occurrence of discoloration is suppressed can be obtained. Discoloration is likely to occur at the end of a polarizing plate, for example, at the end of an image display panel including a polarizing plate, and display performance may be degraded. By forming the chemical modification portion on the end face, occurrence of discoloration can be effectively suppressed. The other portions include not only the surface of the resin film but also the inside of the resin film.
The chemical modification portion may be formed by chemically modifying the resin film. For example, the resin film can be formed by a modification reaction of the hydroxyl groups of the resin film. Examples of the modification reaction of the hydroxyl group of the resin film include substitution with a modification group such as methyl ether, substituted ethyl ether, methoxy-substituted benzyl ether, silyl ether, ester (formate, acetyl, benzoyl), micellar ester, sulfonate, sulfenate, sulfinate, carbonate, carbamate, cyclic acetal, cyclic ketal, cyclic orthoester, silyl derivative group, cyclic carbonate, cyclic borate, and the like. The conditions for the modification reaction may be appropriately selected depending on the type of the modifying group and the like. For example, the resin film is contacted with a chloride of a modification group to be substituted in the presence of a catalyst for 1 minute to 20 hours at 0 ℃ to 100 ℃ as needed to carry out the modification reaction.
The chemical modifier is formed by reacting a hydroxyl group of the resin film with a modifier having a group (a group for improving hydrophobicity) such as an alkyl group, a halogen group, a haloalkyl group, an aryl group, an acyl group, or a silyl group. Chemical modification is performed, for example, by alkylation, halogenation, acylation (e.g., acetylation, esterification), silylation, etherification, etc. These may be used alone or in combination of two or more.
Examples of the acylating agent used in the acylation include carboxylic acid anhydrides, carboxylic acid halides, benzoyl halides, esters, amides, and ketenes. Specific examples thereof include trifluoroacetic anhydride, acetic anhydride, chloroacetyl anhydride, dichloroacetic anhydride, trichloroacetic anhydride, and benzoyl chloride.
Examples of the silylating agent used for the silylation include chlorosilanes such as trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, triphenylchlorosilane, t-butyldimethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilane, and dichlorodiisopropylsilane. As the silylating agent, an amide-based silylating agent such as N, O-bis (trimethylsilyl) acetamide or N, O-bis (trimethylsilyl) trifluoroacetamide, an amine-based silylating agent such as N-trimethylsilylimidazole, or the like may be used.
Examples of the etherifying agent used in the etherification include benzyl bromide, 4-methoxybenzyl chloride, chloromethyl methyl ether and trityl chloride.
In one embodiment, the chemical modification portion has a group containing fluorine. Examples of the group containing fluorine include fluoroalkyl groups having one or more fluorine groups and fluoroacyl groups (for example, trifluoroacetyl groups). Specifically, the chemical modification unit is chemically modified with trifluoroacetic anhydride. In the present embodiment, the end portion 10d including the end face 10c may include fluorine. The width of the end portion containing fluorine (the distance from the end face to the fluorine-containing portion) may be, for example, 1 μm or more, 10 μm or more, or 20 μm or more. On the other hand, the width of the fluorine-containing end portion is preferably 100 μm or less, and may be 50 μm or less. For the end face having the chemical modification, 1787cm in FT-IR spectrum based on ATR measurement -1 The absorbance at 2940cm -1 The ratio of the absorbance is preferably more than 0.2, more preferably 0.25 or more, and still more preferably 0.3 or more. On the other hand, 1787cm -1 The absorbance at 2940cm -1 The ratio of the absorbance is lower than 1, for example. It should be noted thatIn FT-IR spectrum, however, 2940cm -1 The nearby absorption peak is derived from C-H stretching vibration of the resin film, 1787cm -1 The nearby absorption peak is derived from the c=o stretching vibration of the trifluoroacetyl group.
In one embodiment, the chemical modification unit is chemically modified with a silylating agent. In the present embodiment, the end portion 10d including the end face 10c may include silicon. The width of the end portion including silicon (the distance from the end face to the silicon portion) may be, for example, 1 μm or more, 10 μm or more, or 20 μm or more. On the other hand, the width of the end portion containing silicon is preferably 100 μm or less, and may be 50 μm or less.
B. Method of manufacture
The polarizing plate may be obtained by chemically modifying an end face of a resin film containing iodine and having a first main face and a second main face which face each other. In the 1 embodiment, the end face of the resin film is chemically modified in a state where the first protective material is disposed on the first main face of the resin film and the second protective material is disposed on the second main face of the resin film. Specifically, a laminate including a first protective material, a resin film, and a second protective material is prepared, and the end face of the resin film of the laminate is chemically modified. By using such a laminate, for example, the end face of the resin film can be selectively chemically modified.
Fig. 2 is a schematic cross-sectional view showing the outline of the structure of a laminate used for manufacturing a polarizing plate according to the first embodiment of the present invention. The laminate 100 has a first protective material 1, a resin film 10, and a second protective material 2 in this order. The resin film 10 has a first main surface 10a and a second main surface 10b facing each other, the first protective material 1 is disposed on the first main surface 10a of the resin film 10, and the second protective material 2 is disposed on the second main surface 10b of the resin film 10. The first protective material 1 includes a first protective layer 21 and a surface protective film 60 in this order from the resin film 10 side. The second protective material 2 includes, in order from the resin film 10 side, a second protective layer 22, a retardation layer 30, an adhesive layer 40, and a release film (separator) 50.
The surface protective film 60 includes a base material 61 and an adhesive layer 62 formed on one side of the base material 61, and is bonded to the first protective layer 21 so as to be peelable. The retardation layer 30 has a laminated structure including a first retardation layer 31 and a second retardation layer 32. The release film 50 is bonded to the adhesive layer 40 so as to be peelable, and protects the adhesive layer 40. By using the release film 50, for example, roll formation of the laminate 100 becomes possible.
In the example shown in the figure, the retardation layer 30 has a laminated structure including the first retardation layer 31 and the second retardation layer 32, but unlike the example shown in the figure, the retardation layer 30 may have a laminated structure of three or more layers, or may be formed as a single layer.
Fig. 3 is a schematic cross-sectional view showing the outline of the structure of a laminate used in the production of a polarizing plate according to the second embodiment of the present invention. In the second embodiment, the second protective material 2 of the laminate 100 is different from the first embodiment described above in that the second protective layer 22 and the retardation layer 30 are not contained.
The members constituting the laminate may be laminated via any suitable adhesive layer (some of which are not shown). Specific examples of the adhesive layer include an adhesive layer and an adhesive layer. Specifically, the protective layers 21 and 22 are typically bonded to the resin film 10 via an adhesive layer. The retardation layer 30 may be bonded to the second protective layer 22 via an adhesive layer (preferably, an active energy ray-curable adhesive) or may be bonded to the second protective layer 22 via an adhesive layer (for example, an acrylic adhesive). As shown in the figure, when the retardation layer 30 has a laminated structure of two or more layers, the retardation layers are bonded to each other with an adhesive layer (preferably, an active energy ray-curable adhesive) interposed therebetween, for example.
The laminate may be long or monolithic. Here, "long-sized" means: the elongated shape having a length sufficiently long with respect to the width is, for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. The long laminate can be wound into a roll.
B-1. Resin film
The resin film contained in the laminate may be produced by any suitable method. In one embodiment, the method comprises the following steps: hydrophilic polymer films such as polyvinyl alcohol (PVA) films, partially formalized PVA films, and ethylene/vinyl acetate copolymer partially saponified films are subjected to dyeing treatment and stretching treatment with a dichroic substance such as iodine or a dichroic dye. The method may further comprise: insoluble treatment, swelling treatment, crosslinking treatment, and the like. Such a production method is well known and commonly used in the art, and therefore, a detailed description thereof is omitted.
In another embodiment, the resin film contained in the laminate is produced using a laminate of a resin base material and a resin layer (typically, a PVA-based resin layer). For example, it can be manufactured as follows: coating a PVA-based resin solution on a resin substrate and drying the same to form a PVA-based resin layer on the resin substrate, thereby obtaining a laminate of the resin substrate and the PVA-based resin layer; the laminate can be produced by stretching and dyeing. In the present embodiment, it is preferable to form a PVA-based resin layer containing a halogen compound and a PVA-based resin on one side of a resin substrate. Stretching typically comprises the steps of: the laminate was immersed in an aqueous boric acid solution and stretched. Further, the stretching may further include the following steps as needed: before stretching in an aqueous boric acid solution, the laminate is subjected to air stretching at a high temperature (for example, 95 ℃ or higher). In the present embodiment, it is preferable that the laminate is heated while being conveyed in the longitudinal direction, and is subjected to a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction. Typically, the manufacturing method of the present embodiment includes the steps of: the laminate was subjected to an air-assisted stretching treatment, a dyeing treatment, an in-water stretching treatment, and a drying shrinkage treatment in this order. By introducing the auxiliary stretching, even when PVA is coated on the thermoplastic resin substrate, crystallinity of PVA can be improved, and high optical characteristics can be achieved. In addition, since the orientation of PVA is improved in advance, problems such as reduction in orientation and dissolution of PVA can be prevented when immersed in water in the subsequent dyeing step and stretching step, and high optical characteristics can be achieved. Further, when the PVA-based resin layer is immersed in a liquid, disturbance of the orientation of PVA molecules and decrease of the orientation can be suppressed, and high optical characteristics can be achieved, as compared with the case where the PVA-based resin layer does not contain a halogen compound. Further, the laminate is shrunk in the width direction by the drying shrinkage treatment, whereby high optical characteristics can be achieved. The resin substrate may be used as a protective material, may be used as a protective layer for the obtained polarizing plate, or may be peeled off from the laminate of the resin substrate and the PVA-based resin layer. Details of such a method for producing a resin film (polarizing plate) are described in, for example, japanese patent application laid-open No. 2012-73580 and japanese patent No. 6470455. The entire disclosures of these publications are incorporated herein by reference.
B-2. Protective layer
The protective layer is formed of any suitable film that can be used as a protective layer for a polarizing plate. Specific examples of the material to be the main component of the film include cellulose resins such as triacetyl cellulose (TAC), transparent resins such as polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyether sulfone resins, polysulfone resins, polystyrene resins, cycloolefin resins such as polynorbornene resins, polyolefin resins, (meth) acrylic resins, and acetate resins.
As will be described later, the polarizing plate (polarizing plate with retardation layer) obtained from the laminate is typically disposed on the visible side of the image display device, and the first protective layer 21 is disposed on the visible side. Therefore, the first protective layer 21 may be subjected to surface treatments such as Hard Coat (HC) treatment, antireflection treatment, anti-sticking treatment, antiglare treatment, and the like as necessary.
The thickness of the protective layer is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, still more preferably 15 μm to 35 μm. In the case of performing the surface treatment, the thickness of the first protective layer 21 is a thickness including the thickness of the surface treatment layer.
In embodiment 1, the second protective layer 22 disposed between the resin film 10 and the retardation layer 30 is preferably optically isotropic. In the present specification, "optically isotropic" means that: the in-plane retardation Re (550) is 0nm to 10nm, and the retardation Rth (550) in the thickness direction is-10 nm to +10 nm. The thickness of the second protective layer 22 disposed between the resin film 10 and the retardation layer 30 is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, still more preferably 10 μm to 30 μm.
B-3 phase difference layer
The thickness of the retardation layer is also dependent on its composition (being a single layer or having a laminated structure), but is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. On the other hand, the thickness of the retardation layer is, for example, 1 μm or more. When the retardation layers have a laminated structure, the "thickness of the retardation layer" refers to the total thickness of the retardation layers. Specifically, the "thickness of the retardation layer" does not include the thickness of the adhesive layer.
As the retardation layer, an alignment cured layer of a liquid crystal compound (liquid crystal alignment cured layer) is preferably used. By using a liquid crystal compound, for example, the difference between nx and ny of the obtained retardation layer can be increased remarkably compared with a non-liquid crystal material, and therefore, the thickness of the retardation layer for obtaining a desired in-plane retardation can be reduced remarkably. Therefore, the polarizing plate with the retardation layer can be significantly thinned. In the present specification, "orientation-cured layer" means: and a layer in which the liquid crystal compound is aligned in a predetermined direction in the layer and the alignment state is fixed. The term "alignment cured layer" is a concept including an alignment cured layer obtained by curing a liquid crystal monomer as described later. In the retardation layer, typically, rod-like liquid crystal compounds are aligned (parallel alignment) in a state of being aligned along the slow axis direction of the retardation layer.
The above-mentioned liquid crystal alignment cured layer may be formed as follows: the alignment treatment is performed on the surface of a predetermined substrate, and a coating liquid containing a liquid crystal compound is applied to the surface, and the liquid crystal compound is aligned in a direction corresponding to the alignment treatment, and the alignment state is fixed, whereby the alignment layer can be formed. As the orientation treatment, any suitable orientation treatment may be employed. Specifically, a mechanical alignment treatment, a physical alignment treatment, and a chemical alignment treatment can be mentioned. Specific examples of the mechanical orientation treatment include a brushing treatment and a stretching treatment. Specific examples of the physical alignment treatment include a magnetic field alignment treatment and an electric field alignment treatment. Specific examples of the chemical alignment treatment include an oblique vapor deposition method and a photo alignment treatment. The process conditions of the various orientation processes may be any suitable conditions depending on the purpose.
The alignment of the liquid crystal compound is performed by performing a treatment at a temperature showing a liquid crystal phase according to the kind of the liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound is brought into a liquid crystal state, and the liquid crystal compound is aligned according to the alignment treatment direction of the substrate surface.
In one embodiment, the alignment state is fixed by cooling the liquid crystal compound aligned as described above. In the case where the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the alignment state is fixed by subjecting the liquid crystal compound to polymerization treatment or crosslinking treatment.
Specific examples of the liquid crystal compound and the method for forming the alignment cured layer are described in Japanese patent application laid-open No. 2006-163343. The disclosure of this publication is incorporated by reference into this specification.
As described above, the retardation layer may be a single layer or may have a laminated structure of two or more layers.
Unlike the example of the figure, in 1 embodiment in which the retardation layer is a single layer, the retardation layer can function as a λ/4 plate. Specifically, re (550) of the retardation layer is preferably 100nm to 180nm, more preferably 110nm to 170nm, and still more preferably 110nm to 160nm. The thickness of the retardation layer can be adjusted in such a manner as to obtain a desired in-plane retardation of the lambda/4 plate. In the case where the retardation layer is the above-mentioned liquid crystal alignment cured layer, the thickness thereof is, for example, 1.0 μm to 2.5 μm. In this embodiment, the angle between the slow axis of the retardation layer and the absorption axis of the polarizing plate is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and still more preferably 44 ° to 46 °. The phase difference layer preferably exhibits an inverse dispersion wavelength characteristic in which the phase difference value increases according to the wavelength of the measurement light.
In another embodiment, when the retardation layer is a single layer, the retardation layer can function as a λ/2 plate. Specifically, re (550) of the retardation layer is preferably 200nm to 300nm, more preferably 230nm to 290nm, and still more preferably 230nm to 280nm. The thickness of the retardation layer is adjusted so that a desired in-plane retardation of the lambda/2 plate can be obtained. In the case where the retardation layer is the above-mentioned liquid crystal alignment cured layer, the thickness thereof is, for example, 2.0 μm to 4.0 μm. In this embodiment, the angle between the slow axis of the retardation layer and the absorption axis of the polarizing plate is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and still more preferably 12 ° to 16 °.
As shown in the figure, in 1 embodiment of the case where the retardation layer 30 has a laminated structure, the retardation layer 30 has a two-layer laminated structure in which a first retardation layer (H layer) 31 and a second retardation layer (Q layer) 32 are arranged in this order from the resin film 10 side. The H layer typically functions as a lambda/2 plate and the Q layer typically functions as a lambda/4 plate. Specifically, re (550) of the H layer is preferably 200nm to 300nm, more preferably 220nm to 290nm, still more preferably 230nm to 280nm; re (550) of the Q layer is preferably 100nm to 180nm, more preferably 110nm to 170nm, still more preferably 110nm to 150nm. The thickness of the H layer is adjusted in such a way that the desired in-plane retardation of the lambda/2 plate is obtained. When the H layer is the above-mentioned liquid crystal alignment cured layer, the thickness thereof is, for example, 2.0 μm to 4.0. Mu.m. The thickness of the Q layer is adjusted in such a way that the desired in-plane retardation of the lambda/4 plate is obtained. When the Q layer is the above-mentioned cured layer for alignment of liquid crystal, the thickness thereof is, for example, 1.0 μm to 2.5. Mu.m. In this embodiment, the angle between the slow axis of the H layer and the absorption axis of the polarizing plate is preferably 10 ° to 20 °, more preferably 12 ° to 18 °, and still more preferably 12 ° to 16 °; the angle between the slow axis of the Q layer and the absorption axis of the polarizer is preferably 70 ° to 80 °, more preferably 72 ° to 78 °, and still more preferably 72 ° to 76 °. The order of arrangement of the H layer and the Q layer may be reversed, and the angle between the slow axis of the H layer and the absorption axis of the polarizer and the angle between the slow axis of the Q layer and the absorption axis of the polarizer may be reversed. Each layer (for example, H layer and Q layer) may have an inverse dispersion wavelength characteristic in which the phase difference value increases according to the wavelength of the measurement light, a positive wavelength dispersion characteristic in which the phase difference value decreases according to the wavelength of the measurement light, or a flat wavelength dispersion characteristic in which the phase difference value does not substantially change according to the wavelength of the measurement light.
The retardation layer (at least one layer when having a laminated structure) typically shows a relationship of nx > ny=nz in refractive index characteristics. Note that "ny=nz" includes not only the case where ny is completely equal to nz but also the case where ny is substantially equal to nz. Therefore, ny > nz or ny < nz may be present within a range that does not impair the effect of the present invention. The Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3.
As described above, the retardation layer is preferably a liquid crystal alignment cured layer. Examples of the liquid crystal compound include a liquid crystal compound having a liquid crystal phase as a nematic phase (nematic liquid crystal). As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystal property of the liquid crystal compound may be embodied by either dissolution or thermal. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.
In the case where the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (i.e., curing) the liquid crystal monomer. After the liquid crystal monomer is aligned, for example, if the liquid crystal monomers are polymerized or crosslinked with each other, the above-described alignment state can be fixed. Here, the polymer is formed by polymerization, and a three-dimensional network structure is formed by crosslinking, but these are non-liquid crystalline. Therefore, the formed retardation layer does not cause the liquid crystalline compound to change to a liquid crystal phase, a glass phase, or a crystal phase due to a specific temperature change, for example. As a result, the retardation layer is extremely excellent in stability without affecting the temperature change.
The temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on the kind thereof. Specifically, the temperature range is preferably 40℃to 120℃and more preferably 50℃to 100℃and most preferably 60℃to 90 ℃.
As the liquid crystal monomer, any suitable liquid crystal monomer may be used. For example, the polymerizable mesogenic compounds described in Japanese patent application laid-open No. 2002-533742 (WO 00/37585), EP358208 (US 5211877), EP66137 (US 4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445 and the like can be used. Specific examples of such a polymerizable mesogenic compound include, for example, a product name LC242 from BASF corporation, a product name E7 from Merck corporation, and a product name LC-Silicon-CC 3767 from Wacker-Chem corporation. As the liquid crystal monomer, nematic liquid crystal monomer is preferable.
In another embodiment, the retardation layer 30 has a laminated structure of a first retardation layer 31 that can function as a λ/4 plate and a second retardation layer 32 (so-called positive C plate) whose refractive index characteristics show a relationship of nz > nx=ny. Details about the lambda/4 plate are as described above. In this embodiment, the angle between the slow axis of the first retardation layer and the absorption axis of the polarizing plate is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and still more preferably 44 ° to 46 °. The first phase difference layer preferably exhibits an inverse dispersion wavelength characteristic in which the phase difference value increases according to the wavelength of the measurement light.
The retardation Rth (550) in the thickness direction of the positive C plate is preferably-50 nm to-300 nm, more preferably-70 nm to-250 nm, further preferably-90 nm to-200 nm, particularly preferably-100 nm to-180 nm. Here, "nx=ny" includes not only the case where nx and ny are exactly equal but also the case where nx and ny are substantially equal. The in-plane retardation Re (550) of the positive C plate is, for example, below 10nm.
The second phase difference layer having refractive index characteristics of nz > nx=ny may be formed of any suitable material, but is preferably formed of a thin film containing a liquid crystal material fixed in vertical alignment. The liquid crystal material (liquid crystal compound) capable of vertical alignment may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the method for forming the liquid crystal compound and the retardation layer include those described in [0020] to [0028] of JP-A-2002-333642 and methods for forming the retardation layer. In this case, the thickness of the second phase difference layer is preferably 0.5 μm to 5 μm.
B-4. Surface protecting film
The substrate of the surface protective film may be formed of any appropriate material. Specific examples of the forming material include polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); cellulose polymers such as diacetylcellulose and triacetylcellulose; a polycarbonate-based polymer; a (meth) acrylic polymer such as polymethyl methacrylate; cycloolefin polymers such as polynorbornene. These may be used alone or in combination of two or more.
The thickness of the base material of the surface protective film is, for example, 10 μm or more and 100 μm or less, preferably 15 μm or more and 90 μm or less, more preferably 25 μm or more and 80 μm or less.
The pressure-sensitive adhesive layer of the surface protective film may be any suitable one. Specific examples thereof include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, epoxy adhesives, and polyether adhesives. By adjusting the kind, amount, combination and compounding ratio of the monomers forming the base resin of the adhesive, and the compounding amount of the crosslinking agent, reaction temperature, reaction time, and the like, it is possible to prepare an adhesive having desired characteristics in accordance with the purpose. The base resin of the binder may be used alone or in combination of two or more. The base resin is preferably an acrylic resin (specifically, the adhesive layer is preferably composed of an acrylic adhesive). The thickness of the adhesive layer is, for example, 5 μm to 15 μm. The storage modulus at 25℃of the adhesive layer is, for example, 1.0X10 5 Pa～1.0×10 7 Pa。
The thickness of the surface protective film is, for example, 30 μm or more and 100 μm or less.
B-5 adhesive layer
The thickness of the adhesive layer 40 is preferably 10 μm to 20 μm. The adhesive constituting the adhesive layer 40 is similar in detail to the adhesive layer contained in the surface protective film.
B-6 release film
The release film may be formed of any suitable plastic film. Specific examples of the plastic film include polyethylene terephthalate (PET) film, polyethylene film, and polypropylene film. The release film can function as a separator. Specifically, as the release film, a plastic film coated with a release agent on the surface is preferably used. Specific examples of the release agent include silicone release agents, fluorine release agents, and long-chain alkyl acrylate release agents.
The thickness of the release film is preferably 20 μm to 80 μm, more preferably 35 μm to 55 μm.
B-7 preparation of laminate
The laminate according to the embodiment of the present invention can be obtained by disposing the first protective material on the first main surface of the resin film and disposing the second protective material on the second main surface of the resin film. Specifically, each layer constituting the first protective material and the second protective material is laminated on the resin film. Lamination of the layers is performed, for example, while carrying them in rolls (so-called roll-to-roll).
The lamination of the retardation layer is typically performed by transferring a liquid crystal alignment cured layer formed on a substrate. As shown in the figure, when the retardation layers have a laminated structure, each retardation layer may be laminated (transferred) to the resin film in order, or a laminate of the retardation layers may be laminated (transferred) to the resin film. The transfer is performed, for example, with an active energy ray-curable adhesive. The thickness of the cured active energy ray-curable adhesive (the thickness of the adhesive layer) is preferably 0.4 μm or more, more preferably 0.4 μm to 3.0 μm, and still more preferably 0.6 μm to 1.5 μm.
B-8 chemical modification
The chemical modification may be performed by any suitable method, for example, depending on the nature of the modifier to be used. For example, it can be carried out by gas phase reaction. Specifically, the laminate may be placed under an atmosphere containing the gasified modifier. In the case of gas phase reaction, the reaction time is, for example, 30 seconds to 60 minutes. As another example, the reaction may be performed by a liquid phase reaction. Specifically, the laminate (for example, an end face of the laminate) may be coated with a reaction solution containing a modifier, or the laminate may be immersed in the reaction solution containing a modifier. In the case of using a liquid phase reaction by impregnation, the impregnation time is, for example, 10 seconds to 5 minutes.
In the laminate 100 shown in fig. 2, in 1 embodiment, the end portions of the layer (first protective layer) 21 disposed adjacent to the first main surface 10a of the resin film 10 and the layer (second protective layer) 22 disposed adjacent to the second main surface 10b of the resin film 10 are deformed by chemical modification (for example, by dissolution of a modifier), thereby covering the end surface 10c of the resin film 10. Here, the component contained in the layer 21 and the component contained in the layer 22 are preferably deformable by (e.g., soluble in) the modifier. For example, the layers 21 and 22 preferably contain a cellulose resin such as TAC, a polycarbonate resin, a (meth) acrylic resin, a polyester resin, or the like. The material for forming the layer 21 and the layer 22 may be the same or different, but it is preferable that the layer 21 and the layer 22 contain a common component. In the present specification, the term "adjacent" includes the case where the adhesive layer is adjacent to the adhesive layer.
C. Polarizing plate (polarizing plate with phase difference layer)
A polarizing plate (polarizing plate with a retardation layer) obtained by chemically modifying the laminate is typically used for an image display panel. Practically, the obtained polarizing plate (polarizing plate with retardation layer) can be adhered to the image display panel main body through the adhesive layer 40. The release film 50 can function as a separator temporarily bonded until the obtained polarizing plate (polarizing plate with retardation layer) is used.
In the above embodiment, the protective material for the resin film may be used as a product, but is not limited to this. For example, a laminate may be separately prepared using an appropriate protective material and chemically modified, and then the protective material may be removed from the laminate to obtain a polarizing plate, and at least one of the protective layer and the retardation layer may be laminated on the obtained polarizing plate to obtain a polarizing plate.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The thickness is a value measured by the following measurement method. Unless otherwise specified, "parts" and "%" in examples and comparative examples are based on weight.
< thickness >
The thickness of 10 μm or less was measured by a scanning electron microscope (product name "JSM-7100F", manufactured by Japanese electronics Co., ltd.). The thickness exceeding 10 μm was measured by a digital micrometer (manufactured by ANRITSU Co., ltd., product name "KC-351C").
Examples 1 to 1
(production of resin film)
As a thermoplastic resin substrate, an amorphous isophthalic acid copolymerized polyethylene terephthalate film (thickness: 100 μm) having a long-sized form and a Tg of about 75℃was used, and one side of the resin substrate was subjected to corona treatment.
At 9:1 to 100 parts by weight of a PVA-based resin comprising polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (trade name "Gohsefimer" manufactured by Nippon chemical industries Co., ltd.) were added 13 parts by weight of potassium iodide, and the resultant was dissolved in water to prepare a PVA aqueous solution (coating liquid).
The PVA aqueous solution was applied to the corona treated surface of the resin substrate, and dried at 60 ℃ to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The resulting laminate was uniaxially stretched to 2.4 times in the machine direction (lengthwise direction) in an oven at 130 ℃.
Next, the laminate was immersed in an insoluble bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insoluble treatment).
Next, the resulting polarizing plate was immersed in a dyeing bath (aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 60 seconds (dyeing treatment) while adjusting the concentration so that the single-sheet transmittance (Ts) of the polarizing plate finally obtained became a desired value.
Then, the resultant solution was immersed in a crosslinking bath (aqueous boric acid solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40℃for 30 seconds (crosslinking treatment).
Thereafter, the laminate was immersed in an aqueous boric acid solution (boric acid concentration: 4 wt% and potassium iodide concentration: 5 wt%) at a liquid temperature of 70 ℃ and uniaxially stretched (in-water stretching treatment) between rolls having different peripheral speeds so that the total stretching ratio became 5.5 times in the longitudinal direction.
Thereafter, the laminate was immersed in a washing bath (an aqueous solution obtained by mixing 100 parts by weight of water with 4 parts by weight of potassium iodide) at a liquid temperature of 20 ℃ (washing treatment).
After that, while drying in an oven maintained at about 90 ℃, the sheet was brought into contact with a SUS-made heating roller maintained at a surface temperature of about 75 ℃ (drying shrinkage treatment).
Thus, a resin film having a thickness of about 5 μm was formed on the resin substrate, and a laminate having a structure of the resin substrate/the resin film was obtained.
(production of laminate A)
An HC-TAC film (thickness: 32 μm) was bonded to the resin film side of the laminate as a first protective layer by means of an ultraviolet curable adhesive. The HC-TAC film is a film in which a Hard Coat (HC) layer (thickness: 7 μm) is formed on a TAC film (thickness: 25 μm), and is bonded so that the TAC film is on the resin film side. Next, a surface protective film (thickness: 48 μm) was attached to the HC-TAC film. The surface protective film was a film in which an adhesive layer (thickness: 10 μm) was formed on a PET film (thickness: 38 μm). In this way, the first protective material is formed on one side of the resin film.
The resin base material was peeled off from the laminate, and an adhesive layer having a thickness of 15 μm was formed on the other side of the resin film, and a separator (PET film, 38 μm thick) was bonded. Thus, a second protective material was formed on the other side of the resin film to obtain a laminate a.
(chemical modification 1)
The obtained long laminate was cut in the longitudinal direction and the width direction to prepare 10 sheets of 30mm×30mm single-sheet laminate. The longitudinal direction corresponds to the light absorption axis direction of the polarizing plate.
10 sheets of the obtained single sheet-like laminate were stacked, and unfoamed Polystyrene (PS) sheets were disposed on the uppermost surface and the lowermost surface of the laminate, to obtain a laminate assembly.
The laminate assembly obtained and 4ml of trifluoroacetic anhydride (manufactured by FUJIFILM Wako Pure Chemical Corporation and having a purity of 98.0% or more) were placed in a polyethylene bag (a refrigerating bag manufactured by Asahi Kabushiki Kaisha, ziploc (registered trademark)) filled with nitrogen gas, sealed, and left standing at room temperature for 30 minutes.
Thus, a polarizing plate (polarizing plate) was obtained.
Examples 1 to 2
A polarizing plate (polarizing plate) was obtained in the same manner as in example 1-1, except that the above-mentioned standing time was set to 10 minutes in the chemical modification.
Examples 1 to 3
In the case of chemical modification, a polarizing plate (polarizing plate) was obtained in the same manner as in example 1-1, except that the laminate assembly was treated as follows.
(chemical modification 2)
The resulting laminate assembly was immersed in a container (cup) containing trifluoroacetic anhydride at room temperature for 1 minute.
Examples 1 to 4
A polarizing plate (polarizing plate) was obtained in the same manner as in examples 1 to 3, except that dichlorodimethylsilane (purity: 98.0% or more, manufactured by Tokyo chemical Co., ltd.) was used instead of trifluoroacetic anhydride in the chemical modification.
Examples 1 to 5
In the case of chemical modification, a polarizing plate (polarizing plate) was obtained in the same manner as in examples 1 to 4, except that the immersion time was set to 2 minutes.
Examples 2 to 1
A polarizing plate (polarizing plate with a retardation layer) was obtained in the same manner as in examples 1 to 3, except that a laminate was produced in the following manner.
(production of resin film)
A long roll of a polyvinyl alcohol (PVA) film (manufactured by Kuraray under the product name "PE 3000") having a thickness of 30 μm was uniaxially stretched in the longitudinal direction by a roll stretcher so as to be 5.9 times longer than the longitudinal direction, and then subjected to swelling, dyeing, crosslinking, and washing in this order, followed by drying to prepare a resin film having a thickness of 12. Mu.m.
The swelling treatment was carried out in pure water at 20℃while stretching to 2.2 times. Next, the dyeing treatment was carried out while adjusting the weight ratio of iodine to potassium iodide so that the single-sheet transmittance of the obtained polarizing plate became 45.0% to 1: the stretching was performed to 1.4 times while treating in a water solution of 7 at 30 ℃. Then, the crosslinking treatment was carried out in 2 stages, and the crosslinking treatment in stage 1 was carried out in an aqueous solution containing boric acid and potassium iodide at 40℃while stretching to 1.2 times. The boric acid content of the aqueous solution of the crosslinking treatment in the stage 1 was 5.0 wt% and the potassium iodide content was 3.0 wt%. The crosslinking treatment in the 2 nd stage was carried out in an aqueous solution containing boric acid and potassium iodide at 65℃while stretching to 1.6 times. The boric acid content of the aqueous solution of the crosslinking treatment in the 2 nd stage was 4.3 wt% and the potassium iodide content was 5.0 wt%. Next, the washing treatment was carried out with an aqueous potassium iodide solution at 20 ℃. The potassium iodide content of the aqueous solution for the washing treatment was set to 2.6% by weight. Finally, the resin film was obtained by drying at 70℃for 5 minutes.
(preparation of phase-difference layer)
A liquid crystal composition (coating liquid) was prepared by dissolving 10g of a polymerizable liquid crystal (product name: paliocolor LC242, manufactured by BASF Co., ltd., expressed by the following formula) showing a nematic liquid crystal phase and 3g of a photopolymerization initiator (product name: IRGACURE 907, manufactured by BASF Co., ltd.) for the polymerizable liquid crystal compound in 40g of toluene.
The surface of a polyethylene terephthalate (PET) film (thickness: 38 μm) was brushed with a brush cloth to perform an orientation treatment. The orientation process direction is set as: the direction of the absorption axis of the resin film (polarizing plate) when laminated on the resin film was 15 ° when viewed from the visible side. Using a bar coater to apply the aboveThe liquid crystal coating liquid was coated on the alignment-treated surface, and heat-drying was performed at 90 ℃ for 2 minutes, thereby aligning the liquid crystal compound. Irradiating the thus-formed liquid crystal layer with a metal halide lamp at 1mJ/cm 2 The liquid crystal layer was cured to form a liquid crystal alignment cured layer a (H layer) on the PET film. The thickness of the liquid crystal alignment cured layer A was 2.5 μm and the in-plane retardation Re (550) was 270nm. Further, the liquid crystal alignment cured layer a shows nx>ny=nz refractive index characteristic.
A liquid crystal alignment cured layer B (Q layer) was formed on a PET film in the same manner as described above, except that the coating thickness was changed, and the alignment treatment direction was set to 75 ° with respect to the direction of the absorption axis of the resin film (polarizing plate) as viewed from the visual side. The thickness of the liquid crystal alignment cured layer B was 1.5 μm and the in-plane retardation Re (550) was 140nm. Further, the liquid crystal alignment cured layer B shows refractive index characteristics of nx > ny=nz.
(production of laminate B)
An HC-TAC film (thickness: 32 μm) was laminated on one side of the resin film as a first protective layer by means of a PVA based adhesive. The HC-TAC film is a film in which a Hard Coat (HC) layer (thickness: 7 μm) is formed on a TAC film (thickness: 25 μm), and is bonded so that the TAC film is on the resin film side. Next, a surface protective film (thickness: 48 μm) was attached to the HC-TAC film. The surface protective film was a film in which an adhesive layer (thickness: 10 μm) was formed on a PET film (thickness: 38 μm). In this way, the first protective material is formed on one side of the resin film.
A TAC film (thickness: 25 μm) having Re (550) of 0nm was laminated on the other side of the resin film as a second protective layer by means of a PVA based adhesive. Subsequently, the obtained liquid crystal alignment cured layer a (H layer) and liquid crystal alignment cured layer B (Q layer) were sequentially transferred to a TAC film. At this time, transfer (bonding) was performed so that the angle between the light absorption axis of the resin film (polarizing plate) and the slow axis of the alignment cured layer a became 15 °, and the angle between the light absorption axis of the resin film (polarizing plate) and the slow axis of the alignment cured layer B became 75 °. Each transfer was performed with an ultraviolet curable adhesive (thickness 1.0 μm). Then, an adhesive layer having a thickness of 15 μm was formed on the liquid crystal alignment cured layer B, and a separator (PET film, 38 μm thick) was bonded. Thus, a second protective material was formed on the other side of the resin film to obtain a laminate B.
Examples 2 to 2
A polarizing plate (polarizing plate with a retardation layer) was obtained in the same manner as in example 2-1, except that dichlorodimethylsilane was used instead of trifluoroacetic anhydride in the chemical modification.
Example 3
A polarizing plate (polarizing plate with a retardation layer) was obtained in the same manner as in examples 1 to 3, except that a laminate was produced in the following manner.
(production of laminate C)
Laminate C was obtained in the same manner as in example 2-1, except that the resin film having a thickness of 5 μm used in example 1-1 was used instead of the resin film having a thickness of 12. Mu.m.
Comparative example 1
A polarizing plate (polarizing plate) was obtained in the same manner as in example 1-1, except that the obtained laminate was not chemically modified.
Comparative example 2
A polarizing plate (polarizing plate with a retardation layer) was obtained in the same manner as in example 2-1, except that the obtained laminate was not chemically modified.
Comparative example 3
A polarizing plate (polarizing plate with a retardation layer) was obtained in the same manner as in example 3, except that the obtained laminate was not chemically modified.
< evaluation >
For each example and comparative example, durability (discoloration of the end portion) was evaluated. In addition, FT-IR measurement was also performed.
1. Durability (end decolorization)
The surface protective film and the separator were peeled off from the polarizing plates (polarizing plates with retardation layers) obtained in examples and comparative examples, and bonded to a glass plate. In this state, after standing in an oven at 65℃and 90% RH for 240 hours, it was confirmed whether discoloration occurred from the end of the polarizing plate. The validation is performed as follows: the end edge of the polarizing plate in the light absorption axis direction was observed microscopically under cross-transmission (a condition of transmitting polarized incident light in the light absorption axis direction of the polarizing plate). Specifically, the distance (end discoloration width) from the end of the polarizing plate to the position at which the center of the polarizing plate has the same color tone is measured by a microscopic length measurement program by visually determining the position at which the center of the polarizing plate has the same color tone from the end of the polarizing plate.
FT-IR assay
Resin films (polarizing plates) used in examples and comparative examples were prepared separately, and the resin films were subjected to FT-IR measurement under the same conditions as those of examples and comparative examples. Specifically, absorbance was measured by a fourier transform infrared spectroscopic analyzer (trade name "front", manufactured by PerkinElmer corporation) connected to an accessory (manufactured by PerkinElmer corporation, universal ATR Sampling Accessor) capable of performing measurement by the ATR method (total reflection absorption method).
The measurement conditions are as follows.
Incidence angle of infrared light: 45 degree
Resolution: 4cm -1
ATR crystallization: ATR crystal of Ge (refractive index=4.0)
Measurement range: 600cm -1 ～4000cm -1 (ATR crystal of Ge)
Cumulative number of times: 8 times
From the spectrum obtained, 1787cm was calculated -1 Absorbance under (A) 1787 ) Relative to 2940cm -1 Absorbance under (A) 2940 ) Ratio (A) 1787 /A 2940 )。
The evaluation results (end discoloration magnitudes) of the durability are shown in Table 1 and FIGS. 4A to 4C (observations of examples 2-1, 2-2 and comparative example 2). The results of FT-IR measurement are shown in Table 1 and FIG. 5 (examples 1-1, 1-2, 1-3 and comparative example 1).
TABLE 1
As is clear from table 1, discoloration is suppressed by chemical modification. End decolorizing amplitude
Elemental analyses of the end portions of the polarizing plates (samples) obtained in examples 1 to 1 and examples 1 to 5 were performed by a scanning electron microscope (Hitachi High-Tech Co., ltd., product name "S-4800") and an ENERGY dispersive X-ray analysis device (product name "EMAX ENERGY", manufactured by HORIBA Co.). As a result, in example 1-1, fluorine was detected in the vicinity of the end face of the sample, and fluorine was not detected at a position advanced by 30 μm in the in-plane direction from the end face of the sample. In examples 1 to 5, silicon was detected near the end face of the sample, and silicon was not detected at a position pushed by 20 μm in the in-plane direction from the end face of the sample.
In the polarizing plate with the retardation layer of example 2-1, as shown in the cross-sectional SEM observation photograph of fig. 6, it was confirmed that the end face of the polarizing plate pol was covered with the deformed portion (the portion surrounded by the broken line) of the protective layer TAC. Fluorine is detected in the deformed portion (covering portion), and it is considered that the end portion of the protective layer (TAC film) is deformed (specifically, dissolved in the modifier and cured) by chemical modification to cover the polarizer end face. As shown in fig. 6, a deformed portion surrounded by a broken line is continuously formed in the first protective layer TAC and the second protective layer TAC.
In example 3, the same state was confirmed. On the other hand, in examples 1 to 3, the formation of such deformed portions (covering portions) was not confirmed.
Industrial applicability
The polarizing plate according to the embodiment of the present invention is used for an image display device such as a liquid crystal display device, an organic EL display device, or an inorganic EL display device.
Description of the reference numerals
1. First protective material
2. Second protective material
10. Polarizing plate (resin film)
21. First protective layer
22. A second protective layer
30. Phase difference layer
31. First phase difference layer
32. Second phase difference layer
40. Adhesive layer
50. Release film
60. Surface protective film
100. Laminate material
Claims (12)
1. A polarizing plate comprising a resin film containing iodine and having a first main surface and a second main surface which face each other,
the resin film has a chemically modified part on an end face,
the hydrophobicity of the chemical modification part is higher than the hydrophobicity of other parts which are not chemically modified.
2. The polarizing plate according to claim 1, wherein the chemical modification contains a group containing fluorine.
3. The polarizer of claim 2, wherein the fluorine-containing group comprises a trifluoroacetyl group.
4. A polarizing plate according to any one of claims 1 to 3, wherein the chemical modification is chemically modified with trifluoroacetic anhydride.
5. The polarizing plate according to any one of claims 1 to 4, wherein, for the end face, 1787cm in FT-IR spectrum measured based on ATR -1 The absorbance at 2940cm -1 The ratio of absorbance under the condition exceeds 0.2.
6. The polarizing plate according to any one of claims 1 to 5, wherein an end portion including the end face includes fluorine.
7. The polarizing plate according to any one of claims 1 to 6, wherein the chemical modification is chemically modified with a silylating agent.
8. The polarizing plate according to any one of claims 1 to 7, wherein an end portion including the end face comprises silicon.
9. The polarizing plate according to any one of claims 1 to 8, which has a covering portion that covers an end face of the resin film.
10. A method of manufacturing the polarizing plate according to any one of claims 1 to 9, comprising the steps of:
preparing a laminate having a resin film containing iodine and having a first main surface and a second main surface facing each other, a first protective material disposed on the first main surface, and a second protective material disposed on the second main surface; the method comprises the steps of,
the end face of the resin film of the laminate is chemically modified.
11. A polarizing plate is provided with:
the polarizing plate according to any one of claims 1 to 9, and
at least one of the protective layer or the retardation layer.
12. A method for manufacturing the polarizing plate according to claim 11, comprising the steps of:
preparing a laminate having a resin film containing iodine and having a first main surface and a second main surface facing each other, a first protective material disposed on the first main surface, and a second protective material disposed on the second main surface; the method comprises the steps of,
The end face of the resin film of the laminate is chemically modified,
wherein the protective material includes at least one of the protective layer and the retardation layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-059412 | 2021-03-31 | ||
| JP2021059412 | 2021-03-31 | ||
| PCT/JP2022/005325 WO2022209338A1 (en) | 2021-03-31 | 2022-02-10 | Polarizer and method for manufacturing polarizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116806319A true CN116806319A (en) | 2023-09-26 |
Family
ID=83455870
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280013779.3A Pending CN116806319A (en) | 2021-03-31 | 2022-02-10 | Polarizing plate and method for producing polarizing plate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2022158938A (en) |
| KR (1) | KR20230129030A (en) |
| CN (1) | CN116806319A (en) |
| TW (1) | TW202244145A (en) |
| WO (1) | WO2022209338A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4218941B2 (en) * | 2003-02-25 | 2009-02-04 | 日東電工株式会社 | Optical member, manufacturing method thereof, adhesive optical member, and image display device |
| JP4562133B2 (en) * | 2005-04-14 | 2010-10-13 | 日本化薬株式会社 | Polarizing element film, polarizing plate, and manufacturing method thereof |
| US10747025B2 (en) * | 2013-10-17 | 2020-08-18 | Hoya Lens Thailand Ltd. | Polarizing lens, eyewear, and method for manufacturing polarizing lens |
| CN109181186A (en) * | 2018-11-12 | 2019-01-11 | 洪春 | A kind of biodegradable hydrophobicity PVA resin composite materials |
-
2022
- 2022-02-10 JP JP2022019346A patent/JP2022158938A/en not_active Withdrawn
- 2022-02-10 KR KR1020237026457A patent/KR20230129030A/en active Search and Examination
- 2022-02-10 CN CN202280013779.3A patent/CN116806319A/en active Pending
- 2022-02-10 WO PCT/JP2022/005325 patent/WO2022209338A1/en active Application Filing
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| Publication number | Publication date |
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| JP2022158938A (en) | 2022-10-17 |
| KR20230129030A (en) | 2023-09-05 |
| TW202244145A (en) | 2022-11-16 |
| WO2022209338A1 (en) | 2022-10-06 |
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